Process for dyeing or printing fibers from aromatic polyesters



United States Patent US. Cl. 839 9 Claims ABSTRACT OF THE DISCLOSURECinnamoylaminoanthraquinones of the formula Y (H) NH:

in which A is a phenyl radical, which may be substituted for example byhalogen atom, lower alkyl, lower alkoxy or nitro groups X is a hydrogenor halogen atom, or a lower alkyl-, lower alkoxy-, phenoxy-, acyl-,nitro-, cyano-, lower alkyl-mercaptoor phenyl-mercapto-group, one Y is ahydrogen atom and the other Y is a hydrogen atom or a nitro-group yieldvaluable red to blue dyeings of high-fastness-properties on polyesterfibers.

This is a continuation-impart-application of our copending applicationSer. No. 478,757, filed Aug. 10, 1965 now abandoned.

The present invention comprises a process for dyeing or printing fibersfrom aromatic polyester, especially polyethylene terephthalate with acinnamoylaminoanthraquinone of the formula in which A is a phenylradical, which may be substituted for example by halogen atoms, loweralkyl, lower alkoxy or nitro groups X is a hydrogen or halogen atom, ora lower alkyl-, lower alkoxy-, phenoxy-, acyl-, nitro-, cyano-, loweralkyl-mercaptoor phenyl-mercapto-group, one Y is a hydrogen atom and theother Y is a hydrogen atom or a nitro-group.

The present invention comprises also aromatic polyester fibers dyed orprinted with a cinnamoylaminoanthraquinone as defined herein.

The dyestuffs may be obtained by acylating a 1:4-diaminoanthraquinone offormula 3 o NH:

XL g 11TH:

in which X and Y have the significance indicated, with a halide of acinnamic acid. As examples of 1:4 diaminoanthraquinones are mentioned:1:4-diaminoanthraquinone, 1:4-diamino-2-chloro-anthraquinone,1:4-diamino- "ice 2-bromoanthraquinone, 1:4diamino-Z-methoxyanthraquinone, 1:4-diamino-2-phenoxy-anthraquinone,1:4-diamino-2-nitroanthraquinone, 1:4 diamino-Z-methylanthraquinone,1:4-diamino-2-acetylanthraquinone, 1:4-diamino-2-benzoylanthraquinone,1:4-diamino-2-cyanoanthraquinone, 1:4-diamino 2methylmercaptoanthraquinone, 1i4-diamino-2-phenyl/mercaptoanthraquinone, l :4-diamino-5-nitroanthraquinone and 1:4-diamino 2 diamino-Z-bromo-S- or-8-nitroanthraquinone.

The acylating reagents used are preferably the halides, and particularlythe chlorides, of cinnamic acids of the formula.

nooo-on=on in which Z is a hydrogen or halogen atom, or a lower alkyl-,lower alkoxyor nitro-group, and n is an integer having a value of 1 to3. The following carboxylic acids may be quoted as examples: Cinnamicacid, 2-chlorocinnamic acid, 4-chlorocinnamic acid, 2-bromocinnamicacid, 4-bromocinnamic acid, 2:4-dichl0rocinnamic acid,3:4-dichlorocinnarnic acid, 4-methylcinnamic acid, 3:4-dimethylcinnamicacid, 4-isopropylcinnamic acid, 2trifluoromethylcinnamic acid,Z-methoxycinnamic acid, 4- methoxycinnamic acid, 3:4-dimethoxycinnamicacid and 3-nitrocinnamic acid.

I Preferably about 1 mol of the acylating agent is used per mol of1:4diaminoanthraquinone. The acylation can be carried out by knownmethods, for example in an inert organic solvent such as nitrobenzene orchlorobenzene, dimethylformamide or N-methylpyrrolidone, if desired withthe addition of an acid-binding agent, eg. pyridine.

The cinnamoylaminoanthraquinones of the invention have provedparticularly interesting when used for dyeing in admixture with thecorresponding benzoylaminoanthraquinones: substantially more intensecolors are obtained than with the pure benzoylaminoanthraquinone. For 1mol of cinnamoylaminoanthraquinone it is advantageous to use one-thirdto 3 mols, preferably approximately 1 mol, of the appropriatebenzoylarninoanthraquinone. As compared with the1-hydroxy-4-cinnamoylaminoanthraquinone whose use for dyeing polyesterfibers is described in Example 1 of British Patent No. 765,923, and,which gives blotchy dyeings on polyester fibers, the dyestuffs of theinvention are distinguished by their ability to dye polyester fibersuniformly.

In Patent No. 2,155,673 to Miller the 1-amino-2-nitro-4-cinnamoyl-aminoanthraquinone is disclosed as intermediate for vat dyesbut there is no hint in the patent to i the use ofl-arnino-2-nitro-4-cinnamoylanthraquinone as disperse dye.

For dyeing purposes the new dyestuffs are preferably used in finelydivided form, dyeing being carried out with the addition of dispersingagent such as soap, sulfite cellulose waste lye or synthetic detergents,or a combination of different wetting and dispersing agents. It isgenerally advantageous to convert the dyestulf before dyeing into adyestulf preparation which contains a dispersing agent together With thefinely divided dyestuif in a form such that a fine dispersion isproduced on diluting the dyestuif preparation with Water. Such dyestuffpreparations can be obtained in known manner e.g. by reprecipitation ofthe dyestulf from sulfuric acid and grinding of the sludge so obtainedwith sulfite waste lye, and if necessary by grinding the dyestuff inhigh efiiciency grinding equipment, in a dry or wet form, with orwithout the addition of dispersing agent in the grinding process.

To obtain stronger dyeings on polyethylene terephthalate fibers it isgenerally advantageous to add a swelling agent to the dyebath or,especially, to carry out the dyeing process under superatmosphericpressure at a temperature above 100 C., for example, at 120 C. Suitableswelling agents are aromatic carboxylic acid acids, for example, benzoicacid or salicylic acid; phenols, for example, orthoorpara-hydroxydiphenyl; aromatic halogen compounds, for example,chlorobenzene, orthodichlorobenzene or trichlorobenzene;phenylmethylcarbinol or diphenyl. When dyeing under superatmosphericpressure it is advantageous to render the dyebath slightly acid, forexample, by the addition of a weak acid, for example, acetic acid.

Owing to their fastness to alkalis the new dyestuifs are particularlysuited for dyeing by the so-called thermofixing process, in which thematerial to be dyed is impregnated with an aqueous dispersion of thedyestutf, preferably containing 1 to 50% of urea and a thickening agent,particularly sodium alignate, preferably at temperatures of not morethan 60 C., and squeezed in the usual manner. Preferably the impregnatedgoods are squeezed so as to retain an amount of dyeing liquid equivalentto 50 to 100% of their initial weight.

In order to fix the dyestuif the material impregnated in this manner isheated, e.g. in a current of warm air, to temperatures of above 100 C.,for example between 180 to 220 C., preferably after preliminary drying.

The thermofixing process just described is of particular interest in thedyeing of mixed fabrics of polyester fibers and cellulose fibers,particularly cotton. In that case the padding liquid contains, inaddition to the dyestuffs of the invention, dyestuffs suitable for thedyeing of cotton, particularly vat dyestuffs or reactive dyestuffs, i.e.dyestuffs which can be fixed to the cellulose fiber with the formationof a chemical bond, for example dyestuffs containing a chlorotriazine orchlorodiazine group. In the latter case it has proved advantageous toadd an acid binding agent, for example an alkali carbonate, alkaliphosphate, alkali borate or alkali perboate, or mixtures of these, tothe padding solution. When vat dyestuffs are used it is necessary totreat the pad-dyed fabric, after the heat treatment, with an aqueousalkaline solution of a reducing agent to the type used in vat dyeing.

The dyeings obtained are preferably after-treated, for example byheating with an aqueous solution of a non ionic detergent.

The dyestuffs may also be applied by printing intsead of impregnation.For this purpose for example a printing paste is used which in additionto the normal printing additives, such as wetting and thickening agents,contains the finely dispersed dyestufiF, mixed if desired with one ofthe cotton dyestuffs mentioned above, optionally in the presence of ureaand/or an acid-binding agent.

In the following examples the parts and percentages are by weight,unless otherwise stated.

EXAMPLE 1 1 part of 1-amino-2-methoxy-4-cinnamoylamino-anthraquinone iswet ground with 2 parts of a 50% aqueous solution of sulfite cellulosewaste lye and dried.

This dyestufr preparation is stirred with 40 parts of a aqueous solutionof a condensation product of octadecyl alcohol and 20 mols ethyleneoxide, and 4 parts of a 40% acetic acid solution are added. 4,000 partsof a dye bath are prepared from this by dilution with water.

100 parts of cleaned polyester fiber material is placed in this bath at50 C., the temperature raised to 1 130 C., during half-an-hour anddyeing carried out for 1 hour at this temperature with the vesselclosed. Thereafter the material is thoroughly rinsed. A red color ofoutstanding fastness to light and sublimation is obtained.

When a mixture consisting of equal parts of l-amino-Z-methoxy-4-cinnamoylaminoanthraquinone and l-amino-Z-methoxy-4-benzoylaminoanthraquinone is used, the polyester fibers aredyed in strong and even red shades of excellent fastness to light andsublimation.

4 EXAMPLE 2 200 parts of an aqueous dispersion containing 20 parts of1-amino-2-nitro-4-cinnamoylarninoanthraquinone and 2 parts of sodiumdiisobutylnaphthalenesulfonate are poured into a solution of 50 parts ofurea in parts of water and the two thoroughly mixed by means of a highspeed stirrer for a few minutes, with the simultaneous ad dition of 100parts of a 20% sodium carbonate solution, 100 parts of a 5% sodiumalginate solution and 450 parts of water.

A polyethylene terephthalate fabric is pad-dyed with the paddingsolution of obtained at 50 to 60 C. so that the impregnated materialretains an amount of dyestuif solution corresponding to 65 to 70% of itsinitial Weight; it is dried and subsequently heat-treated for 1 minuteat 200 to 220 C.

Thereafter it is washed for 20 minutes at the boil with a solutioncontaining 2 g./l. of a non-ionic detergent and 2 g./l. of anhydroussodium carbonate, rinsed and dried. A blue dyeing of very good fastnessis obtained.

EXAMPLE 3 In the following table in column I other dyestuffs are listed,which, when applied on polyester, fibers are described in the shadesgiven in column II.

Shade on Dyestufii polyester (3) 1 amino 4 cinnamoylaminoanthraquinoneReddish violet, (4) 1 amino 2 -bromo 4 cinnamoylaminoanthraquinone (5)1- amino 2 methyl 4 cinnamoylaminoanthraquinone (6) 1 amino 2 nitro 4cinnamoylaminoanthraquinone (7) 1 amino 2 -acetyl 4cinnamoylaminoanthraquinone (8) 1 amino 2 -cyano 4cinnamoylaminoanthraquinone (9) 1 amino 2 ethoxy 4cinnamoylaminoanthraquinone (10) 1 amino 2 phenoxy 4cinnamoylarninoanthraquinone (11) 1 amino 2 methylmercapto 4cinnamoylaminoanthraquinone Bluish red.

(12) 1 amino 2 phenylmercapto 4 cinnamoylaminoanthraquinone (13) 1-amino 5 nitro 4 cinnamoylaminoanthraquinone (l4) 1 amino 2 brorno 5nitro 4 cinnamoylarninoanthraquinone (15) 1 amino4(m-nitrocinnamoylamino)-anthraquinone Reddish violet (16) 1 amino 4(p-methylcinnamoylamino)-anthraquinone (17) 1 amino 4(p-methoxycinnamoylamino)-anthraquinone (18) 1 amino 4(o-chlorocinnamoylamino)-anthraquinone (19) 1 amino 2bromo-4-(pmethylcinnamoylamino) anthraquinone.

(20) 1 amino 2 bromo-4-(ochlorocinnamoylamino) anthraquinone (21) 1amino 2 chloro-4-cinnamoylaminoanthraquinone Blue.

Reddish.

Red.

Violet.

What is claimed is: 1. A process for dyeing or printing linear polyesterfibers comprising contracting said fibers with acinnamoylaminoanthraquinone of the formula I II I Y o NHCOCH=OHA Y oN112 II I I I I Y 0 NHCOCH=CH-A in which A is a phenyl radical, or aphenyl radical substituted by halogen atoms, lower alkyl, lower alkoxyor nitro groups, X is a hydrogen or halogen atom, or a lower alkyl-,lower alkoxy-, phenoXy-, acyl-, nitro-, cyano-, lower alkylmercaptoorphenylmercapto-group, one Y is a hydrogen atom and the other Y is ahydrogen atom or a nitro-group is used.

2. A process as claimed in claim 1, in which acinnamoylaminoanthraquinone of the given formula is used in which A isthe radical of the formula in which Z is hydrogen or halogen a loweralkyl, lower alkoxy or nitro group and n is an integer from 1 to 3. 3.Aromatic polyester fibers dyed or printed with a dye'stutf of theformula Y O i in which A is a benzene radical, X is a hydrogen orhalogen atom, a lower alkyl-, lower alkoxy-, phenoxy-, acyl-,nitrocyano-, lower alkylmercaptoor phenylmercapto-group, one Y is ahydrogen atom and the other Y a hydrogen atom or a nitro-group.

4. Aromatic polyester fibers dyed or printed with a dyestuif as claimedin claim 3 which A is the radical of the formula in which Z is hydrogenor halogen, a lower alkyl, lower alkoxy or nitro group and n is aninteger from 1 to 3 inclusively 5. Aromatic polyester fibers dyed orprinted with a dyestuff as claimed in claim 3 of the formula (I? NH:

6. Aromatic polyester fibers dyed or printed with a dyestuff as claimedin claim 3 of the formula 7. Aromatic polyester fibers dyed or printedwith a dyestuff as claimed in claim 3 of the formula I i) 1 1HoocH=cH-8. Aromatic polyester fibers dyed or printed with a dyestutf as claimedin claim 3 0f the formula 0 NHz 9. Aromatic polyester fibers dyed orprinted with a dyestuff as claimed in claim 3 of the formula DONALDLEVY, Primary Examiner B. BETTIS, Assistant Examiner US. Cl. X.R. 855

CASE 552l/E/CIP UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONPatent No. 3,503,697 Dated March 31, 1970 Inv n VISVANAIHAN RAMANA'IHANIt is certified that error a ppears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 5, lines 3-9, delete the bracketed formula.

meme) PM) SEALED M522 1973 m1 E0 l m: m- Oonmissionar or Patente-

